Extrusion grade tpe material, its preparation method and application

Abstract

The application discloses an extrusion-grade TPE material and a preparation method and application thereof, and belongs to the technical field of polymer materials. The TPE material provided by the application comprises the following components in parts by mass: 38-72 parts of SEBS resin, 8-32 parts of TPAE resin, 6-14 parts of maleic anhydride graft, and 8-28 parts of paraffin oil. The weight average molecular weight of the SEBS resin is greater than or equal to 260,000. The melt index of the TPAE resin is greater than or equal to 10 g / 10 min under the condition of 230 DEG C and 2.16 kg. The kinematic viscosity of the paraffin oil at 25 DEG C is 8-42 m 2 / s. The TPE material provided by the application is suitable for extrusion by selecting appropriate parts by mass of specific components to cooperate with each other, and the melt index of the obtained TPE material is suitable for extrusion, so that the TPE material can be prepared by extrusion, thereby continuous production can be realized, and the production efficiency is improved. In addition, the obtained TPE material has excellent appearance, high wear resistance and good mechanical properties after extrusion.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of high polymer materials, and particularly relates to an extrusion-grade TPE material and a preparation method and application thereof. BACKGROUND

[0002] Thermoplastic styrene is widely used due to its excellent elasticity, good tensile strength and elasticity, low permanent deformation, excellent flex resistance, good electrical properties and air permeability. However, on the one hand, its high wear resistance is poor, and in the automobile air duct pipe end cap and other parts, due to engine vibration and friction, higher wear resistance is required, and the TPE material cannot be well applied. On the other hand, due to the flowability and melt strength of the existing thermoplastic styrene, it can only be prepared by injection molding in production. However, although the injection molding process can prepare products with complex shapes, it has high process requirements, cannot prepare long-process products and cannot be continuously produced. If the extrusion method is used for preparation, the appearance of the obtained product is poor. SUMMARY

[0003] The present application aims to overcome the shortcomings of the prior art and provide an extrusion-grade TPE material suitable for continuous extrusion preparation, having excellent appearance, good wear resistance and excellent mechanical properties, and a preparation method and application thereof.

[0004] To achieve the above-mentioned purpose, in the first aspect of the present application, the present application provides a TPE material, which comprises the following components by mass:

[0005] 38-72 parts of SEBS resin, 8-32 parts of TPAE resin, 6-14 parts of maleic anhydride graft, 8-28 parts of paraffin oil;

[0006] The weight average molecular weight of the SEBS resin is greater than or equal to 260,000;

[0007] The melt index of the TPAE resin is greater than or equal to 10 g / 10 min at 230℃ under a load of 2.16 kg;

[0008] The kinematic viscosity of the paraffin oil at 25℃ is 8-42 m 2 / s.

[0009] The TPE material provided by the present application can be prepared by extrusion by selecting appropriate mass fractions of specific components to cooperate with each other, and the melt index of the obtained TPE material is suitable, which can be used for continuous production, and is beneficial to improve the production efficiency. And the TPE material obtained has excellent appearance, high wear resistance and good mechanical properties after extrusion.

[0010] Specifically, the application is compounded by selecting SEBS resin with weight average molecular weight ≥ 260,000 and TPAE resin with melt index ≥ 10 g / 10 min under the condition of 230℃, 2.16 kg, and supplemented by maleic anhydride graft and the addition of paraffin oil in a specific range of kinematic viscosity, on the basis of forming a homogeneous phase, due to the flow difference between SEBS resin and TPAE resin, the TPAE resin with good flowability will tend to flow to the flow front during the subsequent extrusion preparation process, forming the outer skin layer, while the SEBS resin with poor flowability is wrapped by the outer layer formed by the TPAE resin to form the inner core layer; therefore, after extrusion molding, a skin-core structure is formed, and the TPE material obtained has excellent wear resistance of the outer skin layer, which can better protect the inner core layer SEBS and provide excellent wear resistance of the product; at the same time, the inner core layer can provide sufficient flexibility for the product, that is, ensure that the product has excellent mechanical properties; the addition of a certain amount of maleic anhydride graft not only helps to achieve the compatibility of SEBS resin and TPAE resin in the early stage, but also can improve the compatibility of the two during the extrusion process, reduce the probability of separation of the inner and outer layers of the TPE material, and ensure good appearance of the product; at the same time, the addition of a proper amount of paraffin oil in a specific range of kinematic viscosity can also help the product to be prepared by extrusion, obtain a product with good appearance, and also help to improve the mechanical properties and wear resistance of the product.

[0011] Exemplarily, the SEBS resin can be any point value or any two-point range value between 38-72 parts, such as 40-70 parts, or 38 parts, 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts, 68 parts, 70 parts, 72 parts, etc.; the TPAE resin can be any point value or any two-point range value between 8-32 parts, such as 10-30 parts, or 8 parts, 10 parts, 13 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, etc.; the maleic anhydride graft can be any point value or any two-point range value between 6-14 parts, such as 7-13 parts, or 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, etc.; the paraffin oil can be any point value or any two-point range value between 8-28 parts, such as 10-25 parts, or 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, etc.

[0012] Preferably, in the TPE material, the mass percentage of SEBS resin is ≥ 33%.

[0013] More preferably, in the TPE material, the mass percentage of SEBS resin is 48-62%.

[0014] It should be noted that the weight average molecular weight of the SEBS resin is tested according to ISO 11344-2016.

[0015] Illustratively, the weight average molecular weight of the SEBS resin can be any point value or any two-point range value greater than or equal to 260,000, such as 260,000-320,000, 260,000-310,000, 260,000-270,000, etc., or can be 260,000, 270,000, 280,000, 290,000, 300,000, 310,000, 320,000, etc.

[0016] The hydrogenation degree of the SEBS resin is greater than or equal to 97%, and the mass percentage of styrene in the SEBS resin is 17-31%.

[0017] It should be noted that the hydrogenation degree and the mass percentage of styrene of the SEBS resin are calculated by nuclear magnetic resonance hydrogen spectrum test.

[0018] The hydrogenation degree and the mass percentage of styrene of the SEBS resin are not particularly limited in the present application, and the effects of the present application can be achieved within the above range.

[0019] It should be noted that the melt index of the TPAE resin under the condition of 230℃, 2.16kg is tested according to ISO 1133-1-2011.

[0020] Illustratively, the melt index of the TPAE resin under the condition of 230℃, 2.16kg can be any point value or any two-point range value greater than or equal to 10g / 10min, such as 10-18g / 10min, 10-16g / 10min, 10-14g / 10min, 10-13g / 10min, etc., or can be 10g / 10min, 11g / 10min, 12g / 10min, 13g / 10min, 14g / 10min, 15g / 10min, 16g / 10min, 17g / 10min, 18g / 10min, etc.

[0021] The TPAE resin comprises i) a polyamide block selected from polyamide-12 (PA-12), polyamide-11 (PA-11), polyamide-6 (PA-6), or a mixture thereof; ii) a polyether block selected from polyether polyols such as polyethylene glycol (PEG), polypropylene glycol (PPG), polytetrahydrofuran (PTHF), or a mixture thereof.

[0022] Preferably, the TPAE resin comprises 10 to 20 polyamide blocks and 10 to 20 polyether blocks.

[0023] It should be noted that the kinematic viscosity of the paraffin oil at 25℃ is tested according to GB / T 265-1988.

[0024] Exemplarily, the kinematic viscosity of the paraffin oil at 25℃ can be any point value or any two-point range value between 8-42m 2 / s, such as 10-40m 2 / s, 17-40m 2 / s, 17-29m 2 / s, 15-20m 2 / s, 10m 2 / s, 12m 2 / s, 14m 2 / s, 16m 2 / s, 18m 2 / s, 20m 2 / s, 22m 2 / s, 24m 2 / s, 26m 2 / s, 28m 2 / s, 30m 2 / s, 32m 2 / s, 34m 2 / s, 36m 2 / s, 38m 2 / s, 40m 2 / s, 42m 2 / s, etc.

[0025] As a preferred embodiment of the TPE material of the present application, the TPE material comprises the following components in parts by mass: 52-60 parts of SEBS resin, 15-20 parts of TPAE resin.

[0026] The present application researches and finds that the proportions of SEBS resin and TPAE resin will affect the wear resistance, mechanical properties and appearance of the product, and when the parts by mass of SEBS resin and TPAE resin are further selected within the above range, the comprehensive effect of the obtained product is more excellent.

[0027] As a preferred embodiment of the TPE material of the present application, the weight average molecular weight of the SEBS resin is 285-305 thousand.

[0028] As a preferred embodiment of the TPE material of the present application, the melt index of the TPAE resin at 230℃, 2.16kg is 13-16g / 10min.

[0029] The research of the present application finds that the weight average molecular weight of the SEBS resin and the melt index of the TPAE resin not only affect the compatibility of the two in the early stage of mixing under the action of the maleic anhydride graft, but also affect the difference in fluidity of the two in the extrusion preparation process, thereby affecting the wear resistance, mechanical properties and appearance effect of the product; when the weight average molecular weight of the SEBS resin and the melt index of the TPAE resin are further selected within the above range, the comprehensive effect of the obtained product is more excellent.

[0030] As a preferred embodiment of the TPE material of the present application, the kinematic viscosity of the paraffin oil at 25 DEG C is 17-29 m 2 / s.

[0031] The research of the present application finds that the range of the kinematic viscosity of the paraffin oil affects the compatibility and fluidity of the components in the extrusion preparation process, and when the kinematic viscosity of the paraffin oil at 25 DEG C is further selected to be 17-29 m 2 / s, the comprehensive performance of the obtained TPE material is more excellent.

[0032] As a preferred embodiment of the TPE material of the present application, the maleic anhydride graft includes at least one of maleic anhydride grafted PP, maleic anhydride grafted POE and maleic anhydride grafted SEBS.

[0033] Preferably, the maleic anhydride graft includes maleic anhydride grafted SEBS.

[0034] The research of the present application finds that the maleic anhydride graft affects the compatibility of the SEBS resin and the TPAE resin, and also affects the bonding force between the inner and outer layer structures of the prepared product, and when the maleic anhydride graft is further selected to be maleic anhydride grafted SEBS, the promotion effect on the compatibility of the SEBS resin and the TPAE resin is more obvious, and therefore the comprehensive performance of the obtained product is more excellent.

[0035] As a preferred embodiment of the TPE material of the present application, the grafting rate of the maleic anhydride graft is 0.5-1.5%.

[0036] It should be noted that the grafting rate of the maleic anhydride graft is obtained by referring to the HG / T 2229-2018 standard test.

[0037] Preferably, the grafting rate of the maleic anhydride graft is 0.8-1%.

[0038] The research of the present application finds that the grafting rate of the maleic anhydride graft affects the compatibility of the SEBS resin and the TPAE resin, and when the grafting rate of the maleic anhydride graft is selected to be 0.5-1.5%, especially 0.8-1%, the comprehensive effect of the obtained product is more excellent.

[0039] As a preferred embodiment of the TPE material of the present application, the TPE material further comprises 0.3-0.6 parts of a light stabilizer and 0.1-0.3 parts of an antioxidant.

[0040] Illustratively, the light stabilizer can be a hindered amine light stabilizer or a triazine light stabilizer. The hindered amine light stabilizer can be at least one of Hostavin® light stabilizer 622, Hostavin® light stabilizer 944, Hostavin® light stabilizer 783, Hostavin® light stabilizer 3853, Hostavin® light stabilizer 292, and Hostavin® light stabilizer 123; and the triazine light stabilizer can be at least one of Chimassorb® UV-234, Chimassorb® UV-236, and Chimassorb® UV-237.

[0041] Illustratively, the antioxidant can be at least one of Irganox® antioxidant 1010, Irganox® antioxidant 1076, Irganox® antioxidant 1790, Irganox® antioxidant 168, Irganox® antioxidant DLTP, and Irganox® antioxidant 626.

[0042] In a second aspect of the present application, the present application further provides a preparation method of the TPE material, which comprises the following steps: mixing and melt-extruding the components to obtain the TPE material.

[0043] As a preferred embodiment of the preparation method of the present application, in the extrusion, the parameters of the twin-screw extruder are as follows: the length-diameter ratio of the twin-screw extruder is (48-54):1, the screw rotation speed is 350-500 rpm, and the extrusion temperature is 180-210°C.

[0044] In a third aspect of the present application, the present application further provides the application of the TPE material in preparing devices in the field of automobiles.

[0045] Illustratively, the application of the TPE material in preparing materials such as automobile air intake pipes and cooling liquid pipes.

[0046] Compared with the prior art, the present application has the following beneficial effects:

[0047] The TPE material provided by the present application can be used for continuous production and is beneficial to improving production efficiency by selecting appropriate mass fractions of specific components to cooperate with each other to obtain a TPE material with a suitable melt index for extrusion preparation. The obtained TPE material has excellent appearance, high wear resistance, and good mechanical properties after extrusion. Specifically, the melt index of the obtained product is below 11.4 g / 10 min. According to the prior art, a melt index below 12 g / 10 min meets the requirements of extrusion grade. That is, the product provided by the present application can be used for long-line extrusion preparation of complex products. The prepared product has a mass loss rate of below 9.9% in the wear resistance test, a tensile strength of above 11.5 MPa, and no peeling in appearance. In addition, the preparation method provided by the present application is simple to operate and is beneficial to actual production. DETAILED DESCRIPTION

[0048] For better illustrating the purposes, technical solutions and advantages of the present application, the present application will be further described in combination with specific examples.

[0049] The reagents, methods and devices used in the present application are all conventional reagents, methods and devices in the art unless otherwise specified; and the raw materials used in parallel experiments are the same batch of raw materials unless otherwise specified.

[0050] SEBS-1: M8555, weight average molecular weight of 285,000, Zhehong;

[0051] SEBS-2: 7533, weight average molecular weight of 305,000, Lichangrong;

[0052] SEBS-3: A1513, weight average molecular weight of 265,000, Ketong;

[0053] SEBS-4: A1633, weight average molecular weight of 325,000, Ketong;

[0054] SEBS-5: 7551, weight average molecular weight of 210,000, Lichangrong;

[0055] TPAE-1: E47-S1, melt index of 13 g / 10 min, Evonik;

[0056] TPAE-2: 3010, melt index of 16 g / 10 min, Xuyang;

[0057] TPAE-3: Pebax 3533, melt index of 11 g / 10 min, Arkema;

[0058] TPAE-4: E62-S31, melt index of 18 g / 10 min, Evonik;

[0059] TPAE-5: 6510, melt index of 5 g / 10 min, Xuyang;

[0060] Maleic anhydride graft 1: maleic anhydride grafted SEBS, GPM5601, grafting rate of 1.0%, Nengzhiguang;

[0061] Maleic anhydride graft 2: maleic anhydride grafted PP, AD-105, grafting rate of 1.15%, Bodichen;

[0062] Maleic anhydride graft 3: maleic anhydride grafted POE, PC-6, grafting rate of 0.9%, Bodichen;

[0063] Maleic anhydride graft 4: maleic anhydride grafted SEBS, BCD-1, grafting rate 0.5%, BODEN;

[0064] Paraffin oil 1: white oil, kinematic viscosity at 25℃ 17mm 2 / s, Yuan Cheng Chemical;

[0065] Paraffin oil 2: white oil, kinematic viscosity at 25℃ 29mm 2 / s, Yuan Cheng Chemical;

[0066] Paraffin oil 3: white oil, kinematic viscosity at 25℃ 10mm 2 / s, Yuan Cheng Chemical;

[0067] Paraffin oil 4: white oil, kinematic viscosity at 25℃ 40mm 2 / s, Yuan Cheng Chemical;

[0068] Paraffin oil 5: white oil, kinematic viscosity at 25℃ 5mm 2 / s, Yuan Cheng Chemical;

[0069] Paraffin oil 6: white oil, kinematic viscosity at 25℃ 50mm 2 / s, Yuan Cheng Chemical;

[0070] Antioxidant: antioxidant 1076, commercially available;

[0071] Light stabilizer: mixture of light stabilizer 944 and light stabilizer UV-234 in a mass ratio of 3:2, commercially available;

[0072] The antioxidant and light stabilizer used in the parallel experiments of the examples and comparative examples are consistent.

[0073] Examples 1-16 and comparative examples 1-8

[0074] The examples and comparative examples of the present application provide a TPE material, the component content (parts by weight) of which is shown in Table 1-2;

[0075] Table 1

[0076]

[0077]

[0078] Table 2

[0079]

[0080]

[0081] The preparation method of the TPE material provided in Example 1 is as follows:

[0082] After the dry raw materials are weighed and mixed, they are fed into a twin-screw extruder, extruded, drawn, cooled, cut, and dried to obtain a TPE material.

[0083] The parameters of the twin-screw extruder are as follows: the length-diameter ratio of the twin-screw extruder is 52:1, the screw rotation speed is 350 rpm, and the extrusion temperature is 200℃.

[0084] The preparation method of the TPE material provided in Examples 2-16 and Comparative Examples 1-8 is consistent with that of Example 1, and no related components are added.

[0085] Effect Example

[0086] The performance of the products prepared in the examples and comparative examples is verified in the effect example; the test items include the following aspects:

[0087] 1. Melt index: detected according to the standard method of ISO 1133-1-2011, and the test conditions are 230℃ and 10kg;

[0088] 2. Tensile strength: detected according to the standard method of ISO 37-2017, and the test conditions are 500mm / min;

[0089] 3. Wear resistance: tested according to the standard method A of ISO 4649-2024, and the mass loss rate is recorded;

[0090] 4. Appearance: a screw extruder is used to evaluate the appearance state of the extruded material, and whether the surface of the product is peeled is investigated, and the peeling degree is recorded, limited to 30s of continuous extrusion; if there is no peeling, it is recorded as no peeling; if the peeling area accounts for less than 5% of the total area of the sample, it is recorded as mild peeling; if the peeling area accounts for 5-10% of the total area of the sample, it is recorded as moderate peeling; and if the peeling area accounts for more than 10% of the total area of the sample, it is recorded as severe peeling.

[0091] The test results are shown in Table 3.

[0092] Table 3

[0093]

[0094]

[0095] As can be seen from Table 3, when the technical scheme of the present application is adopted, the melt indexes of the products obtained are all below 11.4 g / 10 min, according to the prior art, the melt index below 12 g / 10 min meets the requirement of extrusion grade, and the products obtained can be used for long-line extrusion preparation of complex products, and the products obtained have excellent appearance, good wear resistance and mechanical properties; specifically, the mass loss rate of the products obtained in the wear resistance test is below 9.9%, the tensile strength is above 11.5 MPa, and the appearance is all free of peeling;

[0096] As can be seen from Examples 1-4 and Comparative Examples 1-4, the mass parts of the components have obvious effects on the properties of the products; when the addition amount of the SEBS resin in Comparative Example 1 is too small, the tensile strength of the product obtained is obviously poor, and the wear resistance of the product obtained is poor, with a mass loss rate of 18.3%; when the mass parts of the SEBS resin and the TPAE resin in Comparative Example 2 are not within the range given in the present application, the melt index of the product obtained is high, the product is slightly peeled, and the wear resistance also shows a poor trend; when the addition amount of the maleic anhydride grafting product in Comparative Example 3 is too large, the wear resistance of the product obtained is poor, and the melt index of the product is too large, which is not suitable for extrusion preparation; when the addition amount of the paraffin oil in Comparative Example 4 is too large, the product obtained is severely peeled, the tensile strength is obviously decreased, and the melt index is significantly increased, which is not suitable for extrusion preparation, and the wear resistance of the product obtained is also obviously poor;

[0097] As can be seen from Examples 1, Examples 5-7 and Comparative Example 5, the weight average molecular weight of the SEBS resin will affect the properties of the product; when the weight average molecular weight of the SEBS resin in Comparative Example 5 is too low, the product obtained is moderately peeled, and the wear resistance is significantly decreased, and the tensile strength also shows a certain decreasing trend; when the weight average molecular weight of the SEBS resin is further selected within the preferred range, the comprehensive properties of the product obtained are more excellent;

[0098] As can be seen from Examples 1, Examples 8-10 and Comparative Example 6, the melt index of the TPAE resin will affect the properties of the product; when the melt index of the TPAE resin in Comparative Example 6 is too low, the product obtained is slightly peeled, the mass loss rate is obviously increased, and the melt index is also obviously increased, which is not suitable for extrusion preparation; when the melt index of the TPAE resin is further selected within the preferred range, the comprehensive properties of the product obtained are more excellent;

[0099] As can be seen from Examples 1 and Examples 11-13, the type and grafting rate of the maleic anhydride grafting product will also affect the comprehensive properties of the product to some extent;

[0100] As can be seen from Example 1, Examples 14-16 and Comparative Examples 7-8, the kinematic viscosity of the paraffin oil also affects the comprehensive performance of the product, when the kinematic viscosity of the paraffin oil in Comparative Example 7 is too low, the melt index of the obtained product is too high, and the mass loss rate of the obtained product also presents a certain increasing trend; when the kinematic viscosity of the paraffin oil in Comparative Example 8 is too high, the obtained product will appear mild peeling phenomenon, and the mass loss rate of the obtained product also increases obviously.

[0101] Finally, it should be noted that the above examples are intended to illustrate the technical solutions of the present application rather than limit the scope of protection of the present application, and although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present application.

Claims

1. An extrusion grade TPE material characterized in that, The TPE material comprises the following components by mass fraction: 38-72 parts of SEBS resin, 8-32 parts of TPAE resin, 6-14 parts of maleic anhydride graft, 8-28 parts of paraffin oil; The weight average molecular weight of the SEBS resin is ≥ 260,000; The melt index of the TPAE resin at 230℃, 2.16kg is ≥ 10g / 10min; The kinematic viscosity of the paraffin oil at 25°C is 8-42 m 2 / s.

2. The TPE material according to claim 1, characterized in that, The TPE material comprises the following components by mass fraction: 52-60 parts of SEBS resin, 15-20 parts of TPAE resin.

3. The TPE material of claim 1, wherein, The weight average molecular weight of the SEBS resin is 28.5-30.5 million.

4. The TPE material of claim 1, wherein, The melt index of the TPAE resin at 230℃, 2.16kg is 13-16g / 10min.

5. The TPE material of claim 1, wherein, The kinematic viscosity of the paraffin oil at 25°C is 17-29 m 2 / s.

6. The TPE material of claim 1, wherein, The maleic anhydride graft comprises at least one of maleic anhydride grafted PP, maleic anhydride grafted POE, maleic anhydride grafted SEBS.

7. The TPE material of claim 1, wherein, The grafting rate of the maleic anhydride graft is 0.5-1.5%.

8. The TPE material of claim 1, wherein, The TPE material further comprises 0.3-0.6 parts of light stabilizer, 0.1-0.3 parts of antioxidant.

9. Process for the production of a TPE material according to any one of claims 1 to 8, characterized in that, The preparation method comprises the following steps: mixing and melt extruding the components to obtain the TPE material.

10. Use of the TPE material according to any one of claims 1-8 in the preparation of devices in the automotive field.

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